The role of nanosized gold particles in adsorption and oxidation of carbon monoxide over Au/Fe2O3 Catalyst

The presence of gold is found to promote the development of weakly bonded (CO)_ad species over the surface of Au/Fe₂O₃ catalyst during interaction with carbon monoxide (CO) or a mixture of carbon monoxide and oxygen. The concentration of these species and the nature of the bonding depend on the gold particle size. No such species are formed for gold particles larger than ∼11 nm or over gold-free iron oxide. The bulk carbonate-like species, formed in the process with the involvement of the hydroxy groups of the support, are merely side products not responsible for the low temperature activity of this catalyst.     

Gold nanoparticles stabilized by a flake-like Al2O3 support

A flake-like alumina with rough surface and small mesopores has been prepared by a hydrothermal method. Remarkably, such alumina was able to stabilize Au nanoparticles, predominantly ∼2.2 nm in size, even up to an annealing temperature of 700°C. The catalytic activity was tested using the CO oxidation model reaction where a complete conversion of 1% CO in air at 30°C was obtained.     

On the mechanism of selective CO oxidation on nanosized Auγ-Al2O3 catalysts

New findings give further information on the mechanism of carbon monoxide selective oxidation over γ-alumina supported nanoparticle sized gold catalysts. a) CO₂ formation, increasing with rising temperature, is observed in the absence of hydrogen and oxygen pointing to a model of active sites consisting of an ensemble of metallic Au atoms and a cationic Au with a hydroxyl group, b) At high temperatures (>200 °C) in excess of H₂, reversed water gas shift (RWGS) reaction results in CO₂ consumption towards CO and H₂O formation. c) Hydrogen strongly influences the interaction of CO on Auγ-Al₂O₃, by weakening the CO adsorption. The presence of hydrogen plays an important role both decreasing the strength of CO bonding and in the prevention of deactivation and regeneration.     

Support effects in the selective gas phase hydrogenation ofp-chloronitrobenzene over gold

The catalytic continuous gas phase hydrogenation of p-chloronitrobenzene (P=1 atm;T=423 K) has been investigated over a series of oxide (Al₂O₃, TiO₂, Fe₂O₃ and CeO₂) supported Au (1 mol %) catalysts. The application of two catalyst synthesis routes,i.e. impregnation (IMP) and deposition-precipitation (DP), has been considered where the DP route generated smaller mean Au particle sizes (1.5-2.8 nm) compared with the IMP preparation (3.5-9.0 nm). The catalysts have been characterised in terms H2 chemisorption and BET area measurements where the formation of metallic Au post-activation has been verified by diffuse reflectance UV-Vis, XRD and HRTEM analyses.p-Chloroaniline was generated as the sole reaction product over all the Au catalysts with no evidence of C-Cl and/or C-NO₂ bond scission and/or aromatic ring reduction. The specific hydrogenation rate increased with decreasing Au particle size (from 9 to 3 nm), regardless of the nature of the support. This response extends to a reference Au/TiO₂ catalyst provided by the World Gold Council. A decrease in specific rate is in evidence for smaller particles (< 2 nm) and can be attributed to a quantum size effect. The results presented establish the basis for the design and development of a versatile catalytic system for the clean continuous production of high value amino compounds under mild reaction conditions.     

Properties of TiO2 support and the performance of Au/TiO2 Catalyst for CO oxidation reaction

Gold catalysts were prepared on TiO₂ supports of different phase structures (i.e., anatase, rutile and biphasic), TiO₂ crystal size (i.e., 9–23 nm), surface and textural properties (i.e., hydration and surface area). The CO oxidation on the gold catalysts was carried out in an operando-DRIFTS set-up equipped with DRIFTS reactor cell connected on-line to CO gas analyser and gas chromatograph enabling real time monitoring of surface reaction and simultaneous reaction rate measurements. Gold catalysts supported on pure anatase TiO₂ were more resistant to sintering compared to catalysts supported on rutile and bi-phasic TiO₂. Besides catalyst sintering, deposition of surface carbonates is an important cause of catalyst deactivation. The best gold catalyst was prepared on 13 nm anatase TiO₂. It displays both increased activity and stability for CO oxidation reaction at room temperature. Surface and textural properties of TiO₂ also play a role on the performance of the Au/TiO₂ catalyst.     

Investigation of the Tribological Properties of Diamond Films

A chemical vapor deposition (CVD) system has been used to produce polycrystalline and nanocrystalline diamond (NCD) films. For biomedical and electronic engineering applications, it is highly desirable to deposit smooth films with decreased crystal size. In general, diamond coatings with a crystal size of 10-100 nm range are known as NCD. There are several ways in which NCD may be deposited including growth from fullerene precursors with argon dilution. Several workers have proposed various mechanisms for the growth process using inert gas dilution to conventional hot filament (HF) or microwave chemical vapor deposition (MWCVD) systems, or NCD growth through the deployment of CO₂/CO or O₂-rich gas environments. However, the use of inert gas dilution, with carbon containing species is the least complex approach to growing nanocrystalline, and more recently, ultrananocrystaline diamond (UNCD). Mechanical properties of UNCD have been determined by nanoindentation, and their nanotribological properties have been measured by nano-scratch and nano-impact testing. The relative importance of toughness (∼E/H ratio) and elastic strain-to-break (∼H/E ratio) of these systems on their behavior in nano-scratch and nano-impact tests is considered, and strategies for optimizing the deposition conditions for enhanced durability under different contact conditions are suggested in this short communication.     

Growth of Au nanocrystals on CdS nanorods

Nanorods of S²⁻ rich CdS were synthesized by a reaction of excess S versus Cd precursors in the presence of ethylene diamine. The photoluminescence (PL) emission from the S²⁻ rich CdS nanorods was broad with a peak at ∼710 nm, which was 40 nm longer in wavelength than the PL peak from Cd²⁺ rich CdS (∼670 nm) nanorods. The influence of surface electron or hole trap states on the luminescent pathway of CdS nanorods will be discussed to explain these shifts in wavelength. Nanocrystals of Au ∼2 nm in size were grown on S²⁻ rich surfaces of CdS nanorods. Significant luminescence quenching was observed from the Au nanocrystals on the CdS nanorods due to interfacial charge separation. Change separation by the Au nanocrystals on the CdS resulted in enhanced photocatalytic degradation of Procion red mix-5B (PRB) dye in an aqueous solution under UV light irradiation.     

Investigation of the active site and the mode of Au/TiO2 catalyst deactivation using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)

CO is a useful probe in the characterization of surface properties of both metal and metal oxide via adsorption. Adsorption of CO was used to monitor the possible active site of an Au/TiO₂ catalyst for the CO oxidation reaction. CO adsorption on the reduced catalyst results in the band at 2104 cm⁻¹ indicative of Au⁰. During the reaction (in the presence of both CO and O₂ present) the band is shifted to higher wave numbers indicating non-competitive adsorption on the surface of Au species. This study also reveals the relationship between the presence of CO (in the absence of oxygen) and the build-up of surface species such as bicarbonates, formates and carbonate species which decreases the activity of the catalyst. The presence of both the reduced and the cationic species of Au seem to be requirement for the activity of the catalyst.     

An unconventional Au/TiO2 PROX system for complete removal of CO from non-reformate hydrogen

Au-based catalysts, generally known for high activity in the selective catalytic oxidation of CO to CO₂ at ambient temperatures, can play a significant role in increasing the fuel cell system’s CO tolerance. In this work, an unconventional CO tolerance method, using an Au/TiO₂ “guard bed”, has been investigated. The system is unconventional in the sense that it does operate as a PROX catalyst, but not in a traditional reformer system configuration. Instead, it has been developed to completely remove CO onboard the vehicle over a wide range, ppm to percentage levels, from impure pressurized H₂-rich gas, i.e. from partially enriched H₂ that would be stored in a fuel tank/cylinder but that would have some CO contamination and would essentially be dry. This set up will allow a reduction in the cost and complexity of conventional “off-board” hydrogen enrichment. The system CO tolerance obtained with the Au/TiO₂ system was compared with state of the art PtRu/C and PtMo/C CO tolerant anode technologies. Catalytic effectiveness in the removal of CO has been directly monitored by both direct analytical measurements and by monitoring the operation of a laboratory fuel cell to which the purified hydrogen stream was passed.     

Obtaining ZrO<Subscript>2</Subscript> + CeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> + TiO<Subscript>2</Subscript>/Ti compositions by plasma-electrolytic oxidation of titanium and investigating their properties

Regularities of the effect produced by Ce₂(SO₄)₃ salt introduced in an aqueous electrolyte containing Zr(SO₄)₂ on the plasma-electrolytic formation of oxide coatings on titanium, their composition, and structure are studied. ZrO₂ + CeO _x + TiO₂ three-phase oxide coatings with a thickness about 10 μm are obtained. The coatings involve ZrO₂ cubic phase. The ZrO₂-to-TiO₂ phase ratio in the coatings can be controlled. The zirconium content in the coatings reaches 20 at %, while that of cerium is 3–5 at %. The surface layer (∼3-nm thick) contains Ce³⁺ (∼30%) and Ce⁴⁺ (∼70%). Pores in the surface part of coatings have diameters around or smaller than 1 μm and are regularly arranged. The obtained systems have a certain catalytic activity with respect to the oxidation of CO to CO₂ at temperatures above 400–450°C. The coatings are corrosion-resistant in chloride-containing environments. The thickness h of coatings depending on the charge Q supplied to the cell is described by the equation h = h ₀(Q/Q ₀) ⁿ , where n = 0.35 and h ₀ is the thickness of the coating formed at Q ₀ = 1 C/cm².     

Densification and mechanical properties of fine-grained Al2O3-ZrO2 composites consolidated by spark plasma sintering

Alumina matrix composites containing 5 and 10 wt% of ZrO₂ were sintered under 100 MPa pressure by spark plasma sintering process. Alumina powder with an average particle size of 600 nm and yttria-stabilized zirconia with 16 at% of Y₂O₃ and with a particle size of 40 nm were used as starting materials. The influence of ZrO₂ content and sintering temperature on microstructures and mechanical properties of the composites were investigated. All samples could be fully densified at a temperature lower than 1400 °C. The microstructure analysis indicated that the alumina grains had no significant growth (alumina size controlled in submicron level 0.66-0.79 μm), indicating that the zirconia particles provided a hindering effect on the grain growth of alumina. Vickers hardness and fracture toughness of composites increased with increasing ZrO₂ content, and the samples containing 10 wt% of ZrO₂ had the highest Vickers hardness of 18 GPa (5 kg load) and fracture toughness of 5.1 MPa m^1/2.     

Investigation of the active site and the mode of Au/TiO2 catalyst deactivation using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)

CO is a useful probe in the characterization of surface properties of both metal and metal oxide via adsorption. Adsorption of CO was used to monitor the possible active site of an Au/TiO₂ catalyst for the CO oxidation reaction. CO adsorption on the reduced catalyst results in the band at 2104 cm⁻¹ indicative of Au⁰. During the reaction (in the presence of both CO and O2 present) the band is shifted to higher wave numbers indicating non-competitive adsorption on the surface of Au species. This study also reveals the relationship between the presence of CO (in the absence of oxygen) and the build-up of surface species such as bicarbonates, formates and carbonate species which decreases the activity of the catalyst. The presence of both the reduced and the cationic species of Au seem to be requirement for the activity of the catalyst.     

The effect of Au/Ag ratios on surface composition and optical properties of co-sputtered alloy nanoparticles in Au–Ag:SiO2 thin films

Gold–silver alloy nanoparticles with various Au concentrations in sputtered SiO₂ thin films were synthesized by using RF reactive magnetron co-sputtering and then heat-treated in reducing Ar + H₂ atmosphere at different temperatures. The UV–visible absorption spectra of the bimetallic systems confirmed the formation of alloy nanoparticles. The optical absorption of the Au–Ag alloy nanoparticles exhibited only one plasmon resonance absorption peak located at 450 nm between the absorption bands of pure Au and Ag nanoparticles at 400 and 520 nm, respectively, for the thin films annealed at 800 °C. The maximum absorption wavelength of the surface plasmon band showed a red shift with increasing Au content. XPS results indicated that the alloys were in metallic state, and they had a greater tendency to lose electrons as compared to their corresponding monometallic state. Moreover, the positive and negative shift of the Au(4f) core-level binding energies was observed for low and high Au concentration, respectively. Also a negative shift of the Ag(3d) binding energies was increased by increasing Au concentration. Diffusion of the particles toward the surface by increasing the temperature has also been illustrated by AFM images. Based on AFM observations, we have found that the particle size reduced from 35 to 20 nm by increasing the annealing temperature from 600 to 800 °C, while particle size increased by increasing Au concentration in films. In addition, lateral force microscopy (LFM) analysis showed that the alloy particles were uniformly distributed on the surface.     

Synthesis of a NiFe2O4 catalyst for the preferential oxidation of carbon monoxide (PROX)

The aim of this work was to study the NiFe₂O₄ spinel catalyst obtained by combustion reaction in the preferential oxidation of carbon monoxide reaction to conversion reactants H₂, CO and O₂ and to conversion products CH₄, H₂O and CO₂. The powders were prepared according to propellants chemical concept and characterized by XRD, TEM and catalytic tests. The XRD pattern shows the characteristic peaks of the spinel phase. The particle size calculated by TEM was 10.7 nm. The catalyst proved to be more selective to reagents for conversion into O₂ (89.5%) at 350 °C.     

Effect of diffusion annealing on the hysteretic properties of sintered Nd-Fe-B magnets

Effect of diffusion annealing on the formation of dysprosium-saturated grain boundaries in sintered Nd-Fe-B magnets has been studied. As a source of diffusion, we used powders of metallic dysprosium, DyCu, DyGa, and Dy₃Co alloys and DyH _x hydride. Plates ∼1 mm thick made of sintered magnets were molded into powders with a particle size from 3 to 500 μm and subsequently annealed in a vacuum at 750–850°C for 0.5–10 h. After annealing, the microstructure and the elemental composition of grains and grain boundaries were studied by scanning electron microscopy. Under optimum annealing conditions, Dy atoms were shown to diffuse preferentially through grain boundaries of the magnets. The coercive force H _c of Nd-Fe-B plates, which were annealed in contact with the DyGa, Dy₃Co and DyH _x powders and subsequently annealed at 550°C, increases by 4–6 Oe; no substantial decrease in the remanence takes place. The increase in the coercive force depends of the powder particle size and temperature and time of diffusion annealing.     

Role of promoting oxide morphology dictating the activity of Au/SiO2 catalyst in CO oxidation

The interfacial interaction of gold nanoparticles deposited on either model SiO₂/Si(100) or high surface area amorphous or mesoporous silica with minute amounts of promoter oxide like “active” FeO_x, TiO₂ and CeO₂ has been discussed. The role of the active oxide, its contribution to the perimeter along the gold nanoparticles has been interpreted. The oxide may invoke electronic interaction and simultaneously the defect structure of oxides likely has a key issue in the formation and stabilization of very small Au particles. The activity of the Au/oxide perimeter depends not only on the size of the Au particles, but also on the size and morphology of the oxide component (likely amorphous structure) regardless of whether it is supporting Au nanoparticles or decorating them. The activity in CO oxidation over Au catalysts is strongly affected by the length of the Au/“active” oxide perimeter which is regarded as the “active interface”. The longer length of the perimeter is evidenced by the enhanced CO oxidation activity.     

Di-(2-ethylhexyl) dithiophosphoric acid surface protected gold nanoparticles: micellar synthesis, stabilization, isolation, and properties

Gold nanoparticles (AuNPs) were synthesized in the organic solution by means of the reduction of HAuCl₄ by hydrazine in reverse micelles of oxyethylated surfactant Triton N-42, with decane as the dispersion medium. To isolate the powder of particles, the micelles were destroyed with chloroform in the presence of di-(2-ethylhexyl) dithiophosphoric acid as a surface protecting agent. According to the results of several experiments, the yield is within the limits of 90–98%, calculated for gold. The obtained preparations are dark blue hydrophobic powders containing aggregated but not agglomerated gold nanoparticles, as well as microcrystals (∼0.08–0.2 μm) of NaCl. The powders get re-dispersed in weakly polar organic solvents with the formation of colloidal solutions. The shape of the nanoparticles is spherical. Their nuclei are gold single crystals with a narrow size distribution; their diameter (d _Au) is about two times as large as the diameter of the aqueous nucleus (d _c) of initial micelles: d _Au = 7.7 ± 1.4 nm (d _c = 3.6 nm) and 8.8 ± 1.5 nm (4.6 nm). The preparations were studied by means of dynamic light scattering, atomic force microscopy, transmission electron microscopy, UV–vis spectroscopy, IR spectroscopy, X-ray powder diffraction, and thermogravimetric and elemental analyses. In the case of the particles with d _Au = 8.8 nm, the product is a mixture of AuNPs and the salt with the molar ratio Au/NaCl ≈ 1:4.54, while the gross composition of AuNPs per one gold atom is estimated as Au(C₁₆H₃₄O₂PS₂Na∙2N₂H₄)_0.16 with the number of gold atoms in one particle ∼21,000.     

载体中ZrO2/Al2O3比对Pt/ZrO2-Al2O3催化剂性能的影响

相比汽油车而言,柴油车具有高效、低油耗的优势已得到广泛应用。本实验以ZrO₂作为改性剂,探究了ZrO₂与Al₂O₃的质量比对催化剂的影响。研究结果表明：随着ZrO₂的加入,Pt粒子先减小后增大;Pt粒子与载体的交互作用先增大后减小。活性实验数据分析表明,ZrO₂的最佳添加量为40 wt%,CO和C₃H₆完全氧化温度分别降低20 _oC 、25 _oC。贵金属在催化剂的分散度以及贵金属与载体的相互作用随着ZrO₂与Al₂O₃质量比的变化而变化。Pt粒子越小,其与载体的交互作用越强,这表明催化剂性能越强。     

Formation of nanometer-sized Au particles on USY zeolites under hydrogen atmosphere

Gold was deposited on ultrastable Y (USY) zeolite using a newly developed method: just mixing an aqueous solution of HAuCl₄ and zeolite at 353 K in which the NH₄⁺ cation reacted with the Cl⁻ in HAuCl₄. Treatment of the Au-loaded USY zeolite in the atmosphere of hydrogen resulted in the formation of Au⁰ nanoclusters with 1.8 nm diameter at 773 K. The size of Au particle was dependent on the type of zeolite support, composition of gas atmosphere, and temperature of calcination, which was correlated with catalytic performance. This study demonstrated the potential use of zeolites with strong Br?nsted acid character as gold supports.     

ZrO2对钼铼合金微观组织与性能的影响

钼铼合金具有优良的力学性能和机加工性能,是电子、核工业等领域关键的结构材料。在钼铼合金中加入氧化锆,形成弥散强化作用,并结合形变强化来提高材料的力学性能。研究发现,合金粉粒度随着ZrO₂含量的增加而减小,在含量为0.7%时晶粒尺寸最细小均匀;ZrO₂颗粒在合金的变形和断裂过程中表现出钉扎效应,显著提升合金的抗拉强度、屈服强度和断后延伸率等力学性能;ZrO₂强化钼铼合金的抗拉强度和断后延伸率在ZrO₂含量为0.7%时达到最高值,随后减少;ZrO₂基本弥散分布在晶界处并与钼基体形成良好结合界面,可以抑制晶界的迁移,提高钼合金的变形抗力。